Two series of WP/Al2O3 catalyst precursors with WP mass loading in the range 18.5%—37.1% were prepared using the impregnation method and mixing method, respectively, and the catalysts were then obtained by temperatur...Two series of WP/Al2O3 catalyst precursors with WP mass loading in the range 18.5%—37.1% were prepared using the impregnation method and mixing method, respectively, and the catalysts were then obtained by temperature-programmed reduction of supported tungsten phosphate (precursor of WP/Al2O3 catatlysts) in H2 at 650℃ for 4h. The catalysts were characterized by XRD, BET, TG/DTA , XPS and 31P MAS-NMR. The activities of these catalysts were tested in the hydrodenitrogenation (HDN) of pyridine and hydrodesulfurization (HDS) of thiophene at 340℃ and 3.0MPa. The results showed that owing to the stronger interaction of the support with the active species, the precursor of WP/Al2O3 catalyst was more difficultly phosphided and a greater amount of W spe- cies was in a high valence state W6+ on the surface of the catalyst prepared by the impregnation method than that by the mixing method. 31P MAS-NMR results indicated that 31P shift from 85% H3PO4 of 2.55×10-4 for WP and 2.57 ×10-4 for WP/γ-Al2O3 catalysts prepared by mixing method. Such WP/Al2O3 catalysts showed higher HDN activi- ties and lower HDS activities than those prepared by the impregnation method under the same loading of WP. WP/γ-Al2O3 catalysts with weak interaction between support and active species were favorable for HDN reaction while the WP/γ-Al2O3 catalysts with strong interaction were favorable for HDS reaction.展开更多
The molecular structures of metal precursors in the impregnating solution were designed so as to prepare efficient Ni Mo/Al_2O_3 hydrodesulfurization(HDS) catalysts. At first, five typical impregnating solutions were ...The molecular structures of metal precursors in the impregnating solution were designed so as to prepare efficient Ni Mo/Al_2O_3 hydrodesulfurization(HDS) catalysts. At first, five typical impregnating solutions were designed; the existing metal precursors, such as [Mo4(citrate)2O11]^(4-)-like, [P2Mo18O62]^(6-)-like and [P2Mo5O23]^(6-)-like species in the solutions were confirmed by laser Raman spectroscopy(LRS). The UV-Vis spectra results indicated that the solutions containing both phosphoric acid and citric acid could change the existing form of nickel species. Five corresponding Ni Mo/Al_2O_3 catalysts were prepared by the incipient wetness impregnation method. The LRS analysis results of dried catalysts showed that the above metal precursors could be partly retained on alumina support after impregnation and drying, although the interface reaction between different metal precursors and alumina support unavoidably took place. Then the catalysts were sulfided and characterized by N2 physisorption, TEM and XPS analyses. The results showed that different metal precursors in impregnating solution could mainly result in the difference in both the morphology of(Ni)Mo S2 slabs and the promoting effect of Ni species. The catalyst prepared mainly with [P2Mo5O23]^(6-)-like species used as precursors exhibited worse dispersion of(Ni)Mo S2 slabs and lower ratio of Ni–Mo–S active phases than the one with [Mo4(citrate)2O11]^(4-)-like species. Promisingly, the catalyst prepared with co-existing [Mo4(citrate)2O11]^(4-)-like, [P2Mo18O62]^(6-)-like and [P2Mo5O23]^(6-)-like species showed better hydrodesulfurization activity for 4,6-DMDBT thanks to its more well-dispersed Ni–Mo–S active phases.展开更多
Molybdenum disulfide（MoS2） has attracted extensive attention as an alternative to replace noble electrocatalysts in the hydrogen evolution reaction（HER）. Here, we highlight an efficient and straightforward ball mi...Molybdenum disulfide（MoS2） has attracted extensive attention as an alternative to replace noble electrocatalysts in the hydrogen evolution reaction（HER）. Here, we highlight an efficient and straightforward ball milling method,using nanoscale Cu powders as reductant to reduce MoS2 engineering S-vacancies into MoS2 surfaces, to fabricate a defectrich MoS2material（DR-MoS2）. The micron-sized DR-MoS2 catalysts exhibit significantly enhanced catalytic activity for HER with an overpotential（at 10 mA cm^-2） of 176 m V in acidic media and 189 m V in basic media, surpassing most of Mo-based catalysts previously reported, especially in basic solution. Meanwhile stability tests confirm the outstanding durability of DR-MoS2 catalysts in both acid and basic electrolytes. This work not only opens a new pathway to implant defects to MoS2, but also provides low-cost alternative for efficient electrocatalytic production of hydrogen in both alkaline and acidic environments.展开更多
基金Supported by the National Natural Science Foundation of China (No.200273011), the National 973 Project (No.G2000048003)and the Beijing Natural Science Foundation (No.2052009).
文摘Two series of WP/Al2O3 catalyst precursors with WP mass loading in the range 18.5%—37.1% were prepared using the impregnation method and mixing method, respectively, and the catalysts were then obtained by temperature-programmed reduction of supported tungsten phosphate (precursor of WP/Al2O3 catatlysts) in H2 at 650℃ for 4h. The catalysts were characterized by XRD, BET, TG/DTA , XPS and 31P MAS-NMR. The activities of these catalysts were tested in the hydrodenitrogenation (HDN) of pyridine and hydrodesulfurization (HDS) of thiophene at 340℃ and 3.0MPa. The results showed that owing to the stronger interaction of the support with the active species, the precursor of WP/Al2O3 catalyst was more difficultly phosphided and a greater amount of W spe- cies was in a high valence state W6+ on the surface of the catalyst prepared by the impregnation method than that by the mixing method. 31P MAS-NMR results indicated that 31P shift from 85% H3PO4 of 2.55×10-4 for WP and 2.57 ×10-4 for WP/γ-Al2O3 catalysts prepared by mixing method. Such WP/Al2O3 catalysts showed higher HDN activi- ties and lower HDS activities than those prepared by the impregnation method under the same loading of WP. WP/γ-Al2O3 catalysts with weak interaction between support and active species were favorable for HDN reaction while the WP/γ-Al2O3 catalysts with strong interaction were favorable for HDS reaction.
基金supported by the National Key Basic Research Program of China(973 Program,2012CB224802)the SINOPEC project(No.114013)
文摘The molecular structures of metal precursors in the impregnating solution were designed so as to prepare efficient Ni Mo/Al_2O_3 hydrodesulfurization(HDS) catalysts. At first, five typical impregnating solutions were designed; the existing metal precursors, such as [Mo4(citrate)2O11]^(4-)-like, [P2Mo18O62]^(6-)-like and [P2Mo5O23]^(6-)-like species in the solutions were confirmed by laser Raman spectroscopy(LRS). The UV-Vis spectra results indicated that the solutions containing both phosphoric acid and citric acid could change the existing form of nickel species. Five corresponding Ni Mo/Al_2O_3 catalysts were prepared by the incipient wetness impregnation method. The LRS analysis results of dried catalysts showed that the above metal precursors could be partly retained on alumina support after impregnation and drying, although the interface reaction between different metal precursors and alumina support unavoidably took place. Then the catalysts were sulfided and characterized by N2 physisorption, TEM and XPS analyses. The results showed that different metal precursors in impregnating solution could mainly result in the difference in both the morphology of(Ni)Mo S2 slabs and the promoting effect of Ni species. The catalyst prepared mainly with [P2Mo5O23]^(6-)-like species used as precursors exhibited worse dispersion of(Ni)Mo S2 slabs and lower ratio of Ni–Mo–S active phases than the one with [Mo4(citrate)2O11]^(4-)-like species. Promisingly, the catalyst prepared with co-existing [Mo4(citrate)2O11]^(4-)-like, [P2Mo18O62]^(6-)-like and [P2Mo5O23]^(6-)-like species showed better hydrodesulfurization activity for 4,6-DMDBT thanks to its more well-dispersed Ni–Mo–S active phases.
基金supported by the National Basic Research of China (2015CB932500 and 2013CB632702)the National Natural Science Fundation of China (51302141, 51501008, U1560103 and 61274015)
文摘Molybdenum disulfide（MoS2） has attracted extensive attention as an alternative to replace noble electrocatalysts in the hydrogen evolution reaction（HER）. Here, we highlight an efficient and straightforward ball milling method,using nanoscale Cu powders as reductant to reduce MoS2 engineering S-vacancies into MoS2 surfaces, to fabricate a defectrich MoS2material（DR-MoS2）. The micron-sized DR-MoS2 catalysts exhibit significantly enhanced catalytic activity for HER with an overpotential（at 10 mA cm^-2） of 176 m V in acidic media and 189 m V in basic media, surpassing most of Mo-based catalysts previously reported, especially in basic solution. Meanwhile stability tests confirm the outstanding durability of DR-MoS2 catalysts in both acid and basic electrolytes. This work not only opens a new pathway to implant defects to MoS2, but also provides low-cost alternative for efficient electrocatalytic production of hydrogen in both alkaline and acidic environments.
